Polyphenolic alkane reserving agents for acrylonitrile polymer base fibers



uct. Y

alloy fibers contain appropriate functional components loLYrHizNoLrC ALKANE nEsERvINo AGENTS FoR AcRYLoNIrRrLn POLYMER BASE nnsERs Allan R. Wtrtnnenbagh, vai., Frederick H. Narren, Can- No Drawing'. Appnctnron any 29, 195s Serial No. 751,654

2z claims; (cl. 8 21) A valuable and significant contribution to the synthetic fiber art has been the development and provision of the nitrile alloy class of fibers. Such man-made fibers are compris-ed essentially of an acrylonitrile polymer base which contains in theV polymer molecule at least about 80 percent by weight of acrylonitrile, advantageously polyacrylonitrile, which has been procuously modified with- .out' sacrifice of or compromise in its basic liber properties by alloying the acrylonitrile polymer base, as it were, with beneficial additamentsor constituents that are adapted to achieve one or more ameliorative ends forthe fiber prod- Primarily, andof exceptional benefit, the nitrile that render the fiber product remarkably and permanently receptive of many kof a` wide variety of dy'estuffs. Because .of this, fn'itrile alloy fibers are readily dyeable to deep andv level sha'des'of lasting coloration by practice of ordinary dyeingV techniques and procedures using the usual materials for the purpose. By their superior attributes in thesel as wellj as other particulars, the vnitrile alloyf fibers a're clearly and easily distinguishable 'from the conventional prototype acrylonitrile polymerffibers, including the usual and well known copolymeric varieties',` with which the art is familiar and whichy are oftentimes referred-to and known as being acrylic fibers. o a Y Predominantly desirable and advantageous members of the nitrile alloy class of synthetic fibers and the like are those, hereinafter more fully delineated, `that are comprised of acrylonitrile polymer substrates and which contain minor integrant proportions of either, or both, various N-vinyl lactam polymers and copolymers or derivatives thereof; N-vinyl-Z-oxazolidinone polymers yand copolymers or derivativesA thereof; or various N-vinyl-3-morpholinone polymers and copolymers or derivatives thereof.

As paradoxal as it may seem, there are instances wherein the exceptional and capacious'receptivity to dyestuffs of nitrile alloy fibers might advantageouslybe restrained or partially or completely diminished in order that such characteristic of the fiber product might be basically altered so as to provide it with a partial or complete degree o f resistance to becoming stained or colored with dyestuifs. a Y

hFor example, `if a stain-free, white fiber productis desired from arfnitrile alloy material, such as a cloth or fabric article, itrwould be advantageous for the nitrile alloy tojbe provided in` such a form as to' befcapablefo'f complete resistance to becoming stained or colored'by dyes or other color-impartingsubstances with which *the nitrile v alloy may come in contact. .Y i

Of at least commensurate practical signiiicancefis'the problem of producing white or two-tone effects on nitrile alloy fibers whenthey are dyed in the presence of other fibers, vsuch as'cellulosics or wool and other `proteinous fibers (both natural and artificial or synthetic inorigin) with which the nitrile alloy fibers may be blended as well as that of `,achieving-'union dyeing or"unif'ormcolor "level vin such fibersI of nitrile alloy fibers that are being ;dyed`with certain dyestuis'so that union-dye'able blends v"nltedf States atert ice might be provided. As is widely appreciated in the art, union-dyeable blends are those that are comprised of diverse liber constituents which are capable of being directly dyed with the same dyestuff or coloring agent or combination of dyestuiis or coloring agents in the same dyeing treatment performed in the same or separate sequential stages or operations to the same or substantially the sam-e uniform and balanced degree of coloration of each of the fibers in the blend. For purposes of achieving theV immediately above mentioned ends, it would be advantageous, as is apparent, for nitril'e alloy fibers' to be provided in such a forrnV that they would have only a partial resistance to orgreservingv action' against dyestuffs and coloring agents, depending on whether diverse or equal tones of coloration are desired in the dyed blend in which it is contained.

Thus, it would be advantageous, and it is the aim and concern of the present invention, to provide nitrile alloy fibers altered or modified with respect to their receptivity for dyestuffs over a range extending from the capability of such altered forms of nitrile alloy fibers to be cornpletely or substantially completely resistant to becoming stained by application of dyestufs to lesser degrees of resistance, advantageous for purposes of achieving twotoned or union-dyeing, as may be desired, in blends of the nitrile alloy fibers with various cellulosic and proteinous fibers, said lesser degrees of resistance to dyestuffs varying through an entire scale, as it were, from slightly to considerable in inverse proportion to their altered degree of dye-receptivity. f

lt is the principal object of the present invention to provide and' makeV available highly efficacious reserving (or dye resisting) agents specific' in their limiting effect or action upon the dye-rcceptivity of nitrile alloy fibers so as t'o be' useful for the several indicated and related purposes upon' and in conjunction with nitrile alloy fibers, particularly those comprising polymerized N-vinyl lactam (especially N-vinylpyrrolidone or N-vinylcaprolactam) or polymerized N-vinyl-Z-oxazolidinone (including especially the unsubstituted and'rnethyl and ethyl ring substituted species) constituents as dye-receptive adjuvants for the fiber, including'unmixed nitrile alloy fibers as well as blends of nitrile alloy fibers with cellulosic orproteinous fibers and yarn, thread, cord and the like and cloth or fabric constructed from such Iibers'o'r fiberblends.

Another object of the invention is to provide, as new a method or means for controlling in the dye-receptivity of nitiile alloy fibers in unmixed or blended' masses or in various constructed orl fabricatedtextile articles or,` as .might be otherwise expressed, a new and improved method for dyeing or controlling the dyeing or nitrile alloy fibers; especially when they are in blended cellulose or proteinous fiber-containing masses so as to achieve'and possibilitate two-tone or union-dyeing effects.

'Iheabove'in'dicated objects, and corollary benefits and advantages, may be achieved pursuant to the comprehension and` practice of the present inventionby applying to a nitrile alloy fiber, particularly one of the indicated highly` .desirable varieties, a minor proportion ofV from about 0,-1 to Vabout 20 percent by Weight, based on the weight of the resulting composition and depending upon the extent of dye-resistance of ,degree of control desired', of a certain variety Vof polyphenolic alkane compound, Vas

hereinafter more fully illustrated, as a dye reserving or dye-resisting agent. As might be anticipated, the degree of control or resistance to dyeing or the extent of modication of the dye-receptivity of the nitrile alloy fiber that may be achieved is in proportion to the quantity of the dye reserving or resisting agent that is applied thereto. Complete or practically complete resistance to dyeing and coloration are generally afforded by heavier applications of the agent, such as those in the neighborhood of from about 10 to 20 percent by weight. A partial or appreciably enhanced resistance to dyeing (or decrease in dye-receptivity) of the nitrile alloy fiber to an extent or degree that is especially beneficial for achieving twotone shades in the dyeing of nitrile alloy fiber blends may be secured by using a reserving quality of the agent on the fiber that is between about 1.5 to 2 to about 10 percent by weight with the specific effect of the agent again being proportional to the quantity applied. Uniondyeing effects in blends of nitrile alloy fibers with cellulosics or proteinous fibers may ordinarily be facilitated by utilizing a balancing quantity of the agent between about 0.1 and 1.5 or 2 percent by weight in order to promote excellent shade balancing of all the diverse filamentary components during the dyeing of the blend, especially when the dyestufls employed have a propensity to build up upon or disporportionately color the nitrile alloy fiber in the blend, as is often the case with certainrdirect or after-treated direct types of dyestuffs when used to dye cellulosic blends of the nitrile alloy fibers and certain acid types of dyestulfs with proteinous blends. In any case, the precise quantity of the reserving agent that is necessary to apply for any particular purpose can be quickly and readily determined by control testing techniques.

The agents are remarkably adherescent upon and substantive to the ntrile alloy fibers and, once applied, remain on the fiber in a generally permanent manner throughout the normal usages and exposures to which the fiber may be put. The dye reserving or resisting agents have no excessive deleterious effect or intolerable influence on the physical aesthetic characteristics and properties of the fibers on which they are applied and may ordinarily be employed for many of a wide variety of uses with relative impurity in this regard. In addition to utilizing the agents for purposes of establishing or augmenting the resistance to staining by dyestuffs and the like of uncolored nitrile alloy fibers, the agents may frequently be employed with considerable benefit upon lalready dyed or colored articles of the fiber t increase or establish their resistance to undesired staining or additional coloration from various sources. For such purpose a heavy, totally resisting application of the agent may most beneficially be made on the colored fiber. Such stain-proofing treatment, incidentally, may also be made on dyed or otherwise colored nitrile alloy fibers that have been pre-treated, prior to dyeing, with lesser, dye-accepting modifying or mere color reserving or balancing applications or doses of the agent in quantities insufficient to achieve a total or absolute (or practically so) dyeing or coloration-resisting effect. Inaddition, as is apparent, the reserving agents may also be used with great advantage for producing white effects in fiber mixtures in piece dyeing such as may be accomplished by printing the reserving agents on the nitrile alloy cloth of fabric goods being dyed followed by the piece dyeing operation.

The reserving or dye-resisting agents of the present invention, as has been indicated, are capable of achieving excellent results in restraining the action of direct and certain acid dyes on nitrile alloy fibers.

The polyphenolic alkane dye reserving or resisting agents that are used so advantageously in conjunction which contains from 3 to about 6 para-hydroxy phenyl groups in its constitution. Such compounds as 1,1,2,2- tetrakis-p-hydroxy-phenyl ethane and l,1,2,2tetrakisp hydroxy-phenyl propane may be used with especial benefit as the polyphenolic alkane reserving agents in the practice of the present invention, as may such other materials as 2,2,4,4-tetrakis-para-hydroxy-phenyl pentane; 2,2,4,4-tetrakis-para-hydroxy-phenyl hexane; tris p hydroxy-phenyl methane; 2,3,3-tris-p-hydroxy-phenyl butane; 2,2,4,4,6,6-hexakis-p-hydroxy-phenyl hexane; and the like. As is apparent, the polyphenolic alkane substances that may be employed as reserving agents in the practice of the invention are of the general structure:

X H((J)Z wherein X, Y and Z are independently selected from the lgroup consisting of hydrogenand p-hydroxy phenyl radicals with the limitation that a total of not less than about 3 and not more than about 6 p-hydroxy phenyl groups can be present in the compound; and wherein n is a number having an average value from 1 to about 6.

It is advantageous for the applicating formulation or composition of the dye-resisting agent that it utilized for deposition of the latter upon the nitrile alloy fibers to contain between about 0.1 and 20 percent by weight, based on the weight of the fiber, of the dissolved or dispersed dye-resisting agent, depending upon the precise quantity of the agent that may be desired to be deposited on the fiber. The actual concentration of the agent with respect to the liquid medium from which it is applied may be much less than the above-indicated values. Since the agents are highly substantive to the nitrile alloy fibers, their precise concentration with respect to the iquid vehicle in the applicating formulation is relatively immaterial. Generally, the applicating formulation of the dye-resisting agent is found to be completely or substantially completely exhausted of the agent so that its precise concentration in the liquid vehicle is not an essential criticality. In most instances, however, it is unneces- Vsary for the applicating formulations to contain more than about 5 percent of the dye-resisting agent, based on the weight of the dry fiber and depending on the type of dyeing procedure used. Suitable application of the dyeresisting agent may be made when the liquor-to-fiber ratio of the applicating formulation to the nitrile alloy fiber being treated is between about 1 and 100 parts of the former to each part by weight of the fiber. More often it is advantageous for such liquor-to-fibers ratio to be between about 2:1 to 50:1, respectively.

Various techniques may be utilized for preparing suitable applicating formulations of the dye reserving or resisting agent. Usually, as is apparent, it is advantageous to apply it from an aqueous liquid dispersion or solution. Such a dispersion may be prepared by making a preliminary or preparatory solution of rthe dye-resisting agent in a liquid in which it is soluble (such as lower aliphatic alcohols, i.e., methanol, ethanol, etc., ketones, aqueous sodium hydroxide or other caustic solutions) and then diluting the initially prepared solution with the desired quantity of water to preparev the final formulation. Most advantageously, especially when the reservwith nitrile alloy bers in the practice of the present n ing'agents are used in conjunction with dyeing treatments on the tibet', the applicating formulation may be prepared and employed directly as part of the liquid vehicle or bath'in vwhich the fibers are contained during thedyeing. Thus, if it is intended to apply the resisting agent prior to dyeing, the applicating formulation may be prepared and used for deposition of the resisting agent as well as to constitute the body of the dye bath in which the dyeing treatment is accomplished. lIn an analogous manner, the dye-resisting agents may be added to dyed fibers in intermediate stages or after completion of dyeing by incorcorporating them in the dye-bath during -textile finish application, the 'dye resisting agentsmayrbe applied to the "bers fromtheir applicating Yformulations by distributing the ,formulation directl-y `to a running strand of the nitrile alloy/ber being treated usinga [.liquid jet or spray of the formulation. VIf desired, fap- Aplicating rollers and equivalent devices may be utilizedl -for such purpose. When the dye-resisting agents arebeling applied to nitrile alloy articlesyincluding articles 'prepared from ber blends that are in the form of -clo'th .or fabric, vthe application may be made during any .sta-ge .of manufacture or dyeingfof such article using ,procedures analogous to. those hereindescribe'd-and dernonstrated. When clothand fabricare being treated, it may frequently be most convenient for the .application to .be made ina manner analogous to conventional j padding treatments.

In order -to further .illustrate the invention but without being limitedvthereto or restricted thereby, the followling examples are given wherein, unless otherwise indicated, all parts and percentagesare to be takenon a weightbasis.

fEcample 1 vuniform blend ofabout A100 vparts of viscose'rayon f tibers `and 100 parts of nitrile alloy bers Vwere treated *by vuniform application thereto of about"-parts of-a Afdyeresis`ting fagent consisting Yof 1,1,'2,2tetrakis(4hy 4vtiroxyphenyl) ethane. The nitrile=alloy'synthetic'bers @in theblend wereabout 3 denier bers vin-staplelengths Vof about ll/z inches.

'-about S'percent on the weight -of the liber (O.WF.) of jpoly-N-vinyllZ-pyrrolidone (PVP) having Fikentscher y "1K-value of Vabout 55. The viscose rayon yarn wasa tvsernidu'll yarn'having'a staple length of about 1-1/2 inches :and a denier of about 3. 'The dye-resisting agent was `of'Diphenyl vRed 4B Supra (Color Index Direct'Re'd 2),

V a direct dyestui, was added to the treating "liquor andthe 'system agitated for about one hour while being Imain- -tained ata temperature'ofv about'70 C. During the "dyeing, 'about'20 partsof sodium-chloride weregradually added to the system. `Atthe termination of` thedyeing, the treated blendwas removed from the dyestuff-containing system, "rinsedy and dried. The nitrile alloy ber was left entinelypnstained and in acompletely white condition. The viscose rayon component,

however, was dyed to a deep and level shade of colora-- tion. In contrast, whenthe foregoing was repeated, ext. ceptingfto -eliminate thel gpreliminary application ofthe vreserving eagentya. full `depth-dyeing. of both iiibers in the eblendfwasobtained.

Example 2 "Thefproeedure of thefrst example is repeated 'int several Separate 'duplications excepting toA use ffnitrile alloy bers prepared from analogous polymer blends of poly- They were comprisedfof polypy x'acrylonitrile in which there `was 'uniformly lincorporated The application of 'the resisting agent togthe te 1 ,Example SUsing the -is'ame'fnitrile alloy f fiber :asin the @first exziample, one partfof tris(phydroxyphenyl) :methane *.was

fdissolvedin 101parts=of.waterfcontaining *A parta-sodium ,carbonate ranhydrous .at 85 C. Two-and one-half parts of a fnitrile alloy'knit goods-and two and one-half parts cotton-plain weave cloth( prescouredfin l percentlgepal CA-solution) Werextreated insa bath containing 150 parts :liquidiwith-l percent.O.W.F. reserving agent, at 50 C.

wirr-a Laundrometer. 'OnefpercentiDiphenyl Red 4B`Supra (Color Index Direct Red 2) Wasadded to the bath fand runat 50 C.;for onephour. The;cottonjwasdycdideep :red'whil'e the nitrileaalloy` remainedwhite.

@Identical results were 'obtained rusing -1,.1 ;2,2 tetraltis t `(f4-hydroxyphenyl) ethane as the reserving agent` p-hydroxyphenyl propanezasthereserving agent.

RWA (Color Index Direct Blue 22), adirect dye. cotton dyeda deep blue,and the nitrile alloy remained white, ,at both 0.8 percentand 1 .6 percentreserve-agent levels.

indicated.

Identical :results were obtained using 22,4,4,-tetrakis ;p-hydroxyphenyLpentane as the reservingagent.

Example 4 f Fifty-.fifty fnitrilefalloyi-cotton blend (using the same nitrile alloy as above) vstriped knit goods weretreated .with l,1,2,2-tetrakisfpfhydroxyphenyl ethane in a ,manner identical to Example 3 above, usingDiphenyl Red 4B Supra, except that 0.8 .percent and 1.6 percent O.W .F.

levels of the reserving `agents were employed. Results were thesame as infExarnple 3 for,-bothconcentrations.

Example 4 was repeated vusing `vI .percent Benzo JBlue The of thebenecial alloying components mentionedvin-,the

foregoing and when any otherof vthe polyphenolic alkane reserving agents indicated to be within the scope of the invention are utilized in place of those lspecicallyiillustrated. Excellent results mayalso be achieved when the resisting agents are applied on unmixed or unblended nitrile alloy fibers for purposes and applications where such technique and mannerof treatment isdesirable and Commensurate results may ,likewise be achieved with other blends of the nitrilealloy fibers, `including blends with cellulosics other thancottonor vis- Cose rayon yarn (such as cuprammonium rayon yarn, cellulose acetate and the like cellulose esters and other cellulosebers of natural or synthetic or artiicialorigin) vas well as blends of the nitrile alloy iibers .with-various proteinous fibers of naturalor synthetic origin, in- Cluding wool, silk libers, zein-proteinbers (such. asthose that are commercially available under the trade-name Vicaraf feather-keratin, casein fibers, protein -iibers landthelike proteinous or so-called Azlon fibers of, nat ural, articial, regenerated, or reconstitutedorigin.

As has been indicated in the foregoing, the nitrile alloy fibers are comprised essentially ofthe mentioned acrylonitrile polymer Ybase which has been modiiedpr alloyed with benelicial additaments vvorconstituents which arev adapted and calculated, to provide the tibe'r product with its peculiar-and unusuallyadvantageousproperties.

acrylonitrile with poly-N-vinyl2lcaprolactam; poly-N- diverseV types. v may be derived from, and originate.with-arnonomereor Various beneiicialadditaments or constituents 4 thatare capable of securing the desirablecharacteristics o'fiwhieh the nitrle Aalloyli'oer is possessed4 maybe any oiseveral For example, the beneiicial constituent mixture of monomers, capable of being converted tor a dye-receptive and possibly., otherwisefunctionakpolyrner p'rcduct,whi h.s gratter black-eepolyrneriged.to and upon thea1readv-tormed and.. with; adtantage, already ,and ,with equal .adyantag e, ,the beneficial constitu??? be a dye-receptive and possibly otherwise functional,

polymeric product with which the essential acrylonitrile base is graft or block copolymerized by graft copolymerization of acrylonitrile or an acrylonitrile monomer Y mixture on or with the already formed functional polymer in order to furnish the fiber-forming polymer product of which the nitrile alloy fiber is composed. Or, as a t suitable and frequently quite satisfactory alternative, the

corporated by any of several suitable procedures with the.

essential acrylonitrile polymer base. Such adjuvants may be homopolymeric, copolymeric or graft copolymeric substances which serve to augment, at least the dyeability of the normally difficult (if not impossible) to dye acrylonitrile polymer base.

Amongst the most beneficial and advantageous of the nitrile alloy fibers are those that are comprised of the essential acrylontrile polymer base, particularly polyacrylonitrile, in which there has been intimately and permanently or substantially permanently incorporated minor proportions of from l or so up to about 20 or so percent by weight, based on the weight of the nitrile alloy composition, of any of the beneficial additaments or constituents adapted to serve the desired purpose and provide the beneficial result. Generally, such beneficial additaments are employed primarily as dye-assisting adjuvants or components. Advantageously, they may be the polymerized products of such azotic monomers, or mixtures thereof, as the several Nvinyl lactams including such broadly related products as the N-vinyl-2-morpholinones; the N-vinyl-2-oxazolidinones; and certain of the N-vinyl-N-methyl-alkyl-sulfonamides. Thus, the nitrile alloy may be comprised of the acrylonitrile polymer base that is prepared by graft or block copolymerization of acrylonitrile or an acrylonitrile-containing monomer mixture upon a minor proportion of an already formed polymer derived from any of the indicated varieties of azotic monomers or their mixtures. Or, as mentioned, it may consist of a graft copolymer product of any of the indicated varieties of azotic monomers on an already formed and preferably already fabricated acrylonitrile polymer base. Advantageously, and frequently with consummate suitability, the nitrile alloy fiber may be comprised of the acrylonitrile polymer base in which there is permanently incorporated by physical blending in minor proportion of any of the polymer products from the specified azotic monomers or mixtures thereof,

primarily as dye-assisting adjuvants.

Such species of nitrile alloy fibers are capable of being accurately described as synergetic and anisotropic chathrates that are composed of a hydrophobic polymer in combination with a hydrophilic polymer. In such varieties of the nitrile alloy fibers (as well as in other of the forms in which they may be obtained) there is a mutually enhancing cooperative union of a highly crystalline polymer which provides strength, durability, wrinkle recovery and `high melting point in the fibers with an usually non-ionic polychelate that provides dye-receptivity as well as moisture regaining powers for the fiber and other aesthetic characteristics that lend to the wearing comfort of textile goods manufactured from the fiber. The nitrile alloy fibers have been described by G. W. Stantonin an article entitled Zefran appearing in the TextilezResearch Journal, volume XXViI, No. 9, for September 1957, pp. 703-712. They have also been recognized as a distinct class of man-made synthetic tex- As indicated, the adjuvant or beneficial constituent in the nitrile alloy" fiber may be Vhomopolymeric in nature or it may be a straight copolymer of any of the azotic monomers specified with other monoand polyfunctional monomers. Adjuvants ofthis variety are tile fibers in Textil Organon, September 1956, at pages Y avancer ordinarily physically blended with the essential acrylonitrile polymer` base in order to secure the desiredI intimate incorporation of the beneficial constituent and the resulting alloying effect in the fiber. Likewise, there may be similarly utilized for physical blending purposes a d juvants or additaments that are graft copolymeric in nature and which consist of various monomers that are graft copolymerized on substrates consisting of polymers of any of the indicated azotic monomers, such as poly- Nvinyllactam substrates; poly-N-vinyl-Z-oxazolidinone substrates and poly-N-vinyl-N-methyl-alkylsulfonamide substrates. Similarly, just as suitably, graft copolymeric additaments may be provided and employed when they consist of any of the specified or closely related azotic monomers (such as Nvinyllactam monomers, Nvinyl- 2-oxazolidinone monomers and Nvinyl-N-methyl alkylsulfonamide monomers graft copolymerized on other functional polymer substrates.

It is usually beneficial for theV polymer products of the azotic functional monomers to be present as the beneficial component in nitrile alloy fibers in an amount that is in the neighborhood or range of from about5 to 15 percent by weight, based on the weight of the nitrile alloy composition. It is frequently quite desirable to employ a homopolymeric Nvinyllactam polymer, such as poly-Nvinylpyrrolidone (which may also be identified as poly-N-vinyl-2-pyrrolidone or, with varied terminology, poly-Nvinyl-Z-pyrrolidinone), poly-N-vinyl caprolactam, or somewhat related thereto, a poly-Nvinyl-3-morpholinone; or a homopolymeric N-vinyl-Z-oxazolidinone or poly-Nvinyl-5-methyl-2-oxazolidinone; or a homopolymeric Nviny1-methylalkylsulfonamide polymer such as homopolymeric N-vinyl-N-methyl-methylsulfonamide; as the polymeric adjuvant that is blended with the essential acrylonitrile polymer base in the nitrile alloy composition. When physically blended "nitrile alloy products are prepared that utilize, as the beneficial additament or constituent, copolymeric or graft copolymeric products of the indicated azotic monomers, it is usually beneficial for the polymeric adjuvants that are employed to be those which are comprised of at least about 50 percent or even as much as 80 or more percent by weight of the products of the indicated constituents derived from the azotic monomers.

In addition to products of N-vinyl-pyrrolidone or N- vinyl caprolactam, other of the N-vinyl (or l-vinyl) lactams which may be utilized include any of those (or their mixtures) that have been described or which are involved in U.S. Patents Nos. 2,265,450; 2,355,454; and 2,371,804. Particular mention may also be made of N- vinyl-5-methyl-pyrrolidone; N-viny1-3,3-dimethyl gamma valerolactam; and N-vinyl piperidone. Particular mention may also be made of somewhat related products derived in any of the ways described from N-vinyl-3- morpholinones of the structure:

H=CH2 wherein each substituent R unit is independently selected from the group consisting of hydrogen, 1 to about 4 carbon alkyl radicals, 6 to about 10 carbon aryl radicals and equivalents thereof.

Similarly, besides unsubstituted N-vinyl-Z-oxazolidinone, other N-vinyl (or 1-vinyl)2oxazolidinone products which may be used as polymeric adjuvants include those derived from monomers represented by the formula:

Ra-O BO .in .which eat least 4.one vof the substituents R1, R3, or ,Rt groups, when itis .not-hydrogen,.mayf,be.a 1 :Lto .about n4 carbon atom alkyl radical orar to-about 11i) carbon monomers may be .mentioned .N-vinylfS-methyl-Zoxazolidinone; N-vinyl-S-chloromethyl-Z-oXazolidinone; `N vinyl-4,5-dimethyl-Z-oxazolidinone, N-vinyl-S-ethyl 2 oxazolidinone; Nvinyl-5phenyl-Z-oxazolidinone; and the like.

The N-vinyl N m'ethyle'alkylsulfonamide monomers whose polymeric products may be advantageously utilized for the nitrile alloys include those represented by the formula:

1lb-CHI .y nHC=C`H3 A wherein R is hydrogen, a A1 to.about 4.carbon.alkyl.radical,

va i6 to about 10-carbon aryl radical for'some-equivalent thereof.

Suitable nitrile'alloy products may also be manufactured `from other beneicial additaments :or components that aremore or less-equivalentgto those derived from .the

azotic monomers indicated inthe foregoing. Thus, `.other `varieties of N-heterocyclic monomers more or less similar or-related to the speced .N-2-propenyl .types .andanalogous related azotic compounds may frequently be employed Vin combination with or to replace .the several beneficial additaments or constituents that have been delineated.

What is claimed is: ,1. `A synthetic textile fiberwhich is characterizedrin vhaving its normal receptivity 'to dyestulszmodiedxsoas to have dye-resisting characteristics, ,said ber beingselected from `the class ofsynthetic vtextile tibersconsisting of (A) intimate polymer blends comprised .essentially `of (Al) between about 80 and about 99 -weight percent, based on .dry ber weight, of .aber-forming.acrylonitrile addition polymer with (A2) between .about.20.and :about 1 weight percent, based on `dry fiber weight, of..an azot'ic polymeric dye-assisting adjuvant .selectedfromzthe Ygroup consisting of addition polymers .of atleast. about 50-weight percent, based on the weight of the vazoti: polymer,of

(A2a) N-vinyl lactam monomers; v(2`b) N-vinyl-3-morpholinone `monomers of the structure:

in which R1, R2, R3 and R., are independently selected from the group consisting of hydrogen, l to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A2d) N-vinyl-N-methyl-alkylsulfonamide monomers of the structure:

- o ll R-e=o N-CHa HC=CH2 wherein R selected from the group consisting of hyeast-.see

Iri.roger 1,.,1 .to .about =4 carbon atom falkylsubstituents :and

6to-about .10 .carbon atom zarylsubstituents; and (A22) ,pre-.formed ,tbenforming acrylonitrile addition ,polymer .substrate with `graft copolymerized substituents -thereon of (B2) between about 20 and about l weight percent,

.based-.on dry rfiber weight, of addition :polymerized azotic Y r.monomer .substituents `of at least about .50 weightpercen-t, based on the weight of `graft copolymerized Vsubstituent, of (B2a) N-vinyl lactam monomers; (B2b);said N-vinyl-.3morpholinone monomers; (B2e) `sanda-vinyl- -2-o1tazolidinonemonomers; (B2d) said'N-vinyl-.N-methyllalk-ylsulfonamide monomers and (B2e) mixtures there of; and` (C) Aliber-forming graft copolymers comprised essentially .of'(C1) between about 80 and `9 weig'ht percent, based on'dry liber weight, of acrylonitrile graft Vopolymerize'd'on (C2) between about 20 and about 1 weightrpercent, lbased on dry ber weight, of a pre-formed, dye-assistingazotic addition polymer substrate of atleast about I50 weight percent, based on the weight of `said substrate, of (C2a) N-vinyl lactam monomers; (.C2b) Asaid .N-vinyl-3-morpholinone monomers; (C2c) said N- vinyl-rZ-.oxazolidinone monomers; (C2d) said N-vinyl-.N- methyl-alkylsulfonamide monomers; and (C2e) mixtures thereof, said liber containing as a dye reserving and resisting agent .etfective against direct and acid dyestuffs between about 0.1 and 20 percent by weight, based on the weight .of .the fiber, of a compound having the for mula: t

t H(C)z n wherein X, Y and Z vare independently Vselected from Athe groupfconsisting of hydrogen and p-hydroxy phenyl radicals with thelimitation that a .totalof not less Vthan ning action .to becoming .stained u pon lbeing contacted-.with

d yestufts.

4. .The treated .fiber of claim 1 containing between Vabout .10 and Vabout .2O percent by weight of lsaid .re-

serving agent and characterized in having a substantially complete resistance to becoming stained upon contactA S. The treated ber of'claim "1 contained in a blend of bers with cellulosic '.tbers.

6. A blend of fibers in-accordance with the blend set forth in claim 5, wherein said cellulosic fibers are cotton.

7. The treated ber of claim 1 contained in a blend of fibers with proteinous bers.

8. A blend of fibers in accordance with the blend set forth in claim'7, wherein said proteinous bers are wool.

9. The treated `fiber of claim l, wherein-said synthetic liber contains polymerized N-vinyl lactam monomer.

10. The treated fiber of claim 1, wherein said syn-V `thetic fiber contains polymerized N-vinyl-2-oxazolidinone 12. The treated ber of claim 1, wherein said syn` thetic liber consists of an intimate polymer blend of polyacrylonitrile and poly-N-vinyl-2-pyrrolidone asa dye-V assisting adjuvant.

`- i13. The treated ber of claim 1. wherein said Synthetic liber consists of an intimate polymer blend of polyacrylonitrile and poly-N-vinylcaprolactam as a dye-assisting adjuvant.

14. The treated liber of claim 1, wherein said synf thetic liber consists of an intimate polymer blend of polyacrylonitrile and poly-N-vinyl-S-methyl-Z-oxazolidinone as a dye-assisting adjuvant.

15. The treated ber of claim 1, wherein said synthetic ber consists of an intimate polymer blend of poly- `acrylonitrile and poly-N-vinyl-Z-oxazolidinone as a dye- 'assisting adjuvant.

16. The treated fiber of claim 1, wherein said synthetic fiber consists of an intimate polymer blend of jpolyacrylonitrile and poly-N-vinyl-3-morpholinone as a f dye-assisting adjuvant.

17. The treated article of claim 1, wherein said dyeresisting agent is 1,1,2,2-tetrakis 4hydroxyphenyl ethane.

18. The treated article of claim 1, wherein said dyevresisting agent is tris(p-hydroxyphenyl)methane.

i 19. The treated article of claim 1, wherein said dye- -resisting agent is 1,l,2,2-tetrakis-p-hydroxy-phenyl propane.

20. The treated article of claim 1, wherein said dye- `resisting agent is 1,1,2,2-tetrakis-p-hydroxy-phenyl-pentane.

21. The treated article of claim 1, wherein said dyefresisting agent is 1,1,2,2-tetrakis-p-hydroxy-phenyl-hex- -ane.

22. Treatment for a synthetic fiber to reduce its re' tion polymer with (A2) between about 20 and about 1 weight percent, based on dry liber weight, of an azotic polymeric dye-assisting adjuvant selected from the group Vconsisting of addition polymers of at least about 50 'weight percent, based on the weight of the azotic polymer, of (A2a) N-vinyl lactam monomers; (A2b) N- Vvinyl-3-morpholinone monomers of the structure:

non non non /c=o wherein each substituent R unit is independently selected,

from the group consisting of hydrogen, 1 to about 4 car- .,bon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A2c) N-vinyl-Z-oxazolidinon -monomers of the structurei vso 12 "inlwhich R1, R2, VR5 and R4 are independently selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A2d) N-vinyl-N-methyl-alkylsulfonamide monomersv of the structure:

'wherein R is selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; and (A2e) mixtures thereof; (B) fiber-forming graft copolymers comprised essentially of (B1) between about 80 and about 99 weight percent, based on dry ber weight, of a pre-formed ber-forming acrylonitrile addition polyvmer substrate with graft copolymerized substituents thereon of (B2) between about 20 and about 1 weight percent, based on dry fiber weight, of addition polymerized azotic monomer substituents of at least about 50 weight percent, based on the weight of graft copolymerized substituent, of (B2a) N-vinyl lactam monomers; (B2b) said N-vinyl-3-morpholinone monomers; (B2C) said N-vinyl-2-oxaz0lidinone monomers; (B2d) said N- vinyl-N-methyl-alkylsulfonamide monomers; and (B2e) mixtures thereof; and (C) fiber-forming graft copolymers comprised essentially of (Cl) between about and 99 weight'percent, based on dry fiber weight,rof acrylonitrile graft ycopolymerized on (C2) between about 20 and about 1 weight percent, based on dry fiber weight, of a `'pre-forr'ne'.d, dye-assisting, azotic addition polymer substrate of at least about 50 weight percent, based on the ,weight of-s'aid substrate, of (C211) N-vinyl lactam monor'ners; (C2b) said N-vinyl-S-morpholinone monomers (CZc) said N-vinyI-2-oxazo1idinone monomers; (C2d) Asaid N-vinyl-N-methyl-alkylsulfonamide monomers; and (C2e) mixtures thereof, which treatment comprises applying tothe ber between about 0.1 and 20 percent by weight on the weight of the fiber of a dye-resisting agent effective against direct and acid dyestuls as dened by Formula1 in claim 1.

References Cited in the le of this patent UNITED STATES PATENTS 2,623,806 Fuchs Dec. 30, 1952 FOREIGN PATENTS 759,595 Great Britain Oct. 24, 1956 OTHER REFERENCES Sandoz: J.S.D.C., vol. 66, October 1950, p. 564. 

1. A SYNTHETIC TEXTILE FIBER WHICH IS CHARACTERIZED IN HAVING ITS NORMAL RECEPTIVITY TO DYESTUFFS MODIFIED SO AS TO HAVE DYE-RESISTING CHARACTERISTICS, SAID FIBER BEING SELECTED FROM THE CLASS OF SYNTHETIC TEXTILE FIBERS CONSISTING OF (A) INTIMATE POLYMER BLENDS COMPRISED ESSENTIALLY OF (A1) BETWEEN ABOUT 80 AND ABOUT 99 WEIGHT PERCENT, BASED ON DRY FIBER WEIGHT, OF A FIBER-FORMING ACRYLONITRILE ADDITION POLYMER WITH (A2) BETWEEN ABOUT 20 AND ABOUT 1 WEIGHT PERCENT, BASED ON DRY FIBER WEIGHT, OF AN AZOTIC POLYMERIC DYE-ASSISTING ADJUVANT SELECTED FROM THE GROUP CONSISTING OF ADDITION POLYMERS OF AT LEAST ABOUT 50 WEIGHT PERCENT, BASED ON THE WEIGHT OF THE AZOTIC POLYMER, OF (A2A) N-VINYL LACTAM MONOMERS, (A2B) N-VINYL-3-MORPHOLINONE MONOMERS OF THE STRUCTURE: 